Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN POLYEPOXIDE TREATED DERIVATIVES OBTAINED BY REAC- TION OF MONOEPOXIDES WITH RESINS Melvin De Groote, University City, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application April 22, 1953, Serial No. 350,533

20 Claims. (Cl. 252-338) The present invention is a continuationin-part of our co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-inoil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine drplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the invention.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Attention is directed to two co-pending De Groote applications, Serial No. 310,553, filed September 19, 1952, now Patent No. 2,695,889, and Serial No. 333,389, filed January 26, 1953. These two applications described hydrophile products obtained by the oxyalkylation of condensates of certain phenol-aldehyde resins with basic non-hydroxylated polyamines and formaldehyde.

The present invention is concerned with the breaking of water-in-oil emulsions by the use of products of reaction obtained by a 3-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic nonia, Patented Nov. 20, 1956 the divalent 0 L radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent dis'ulfide radical S-S-; and R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol by the use of such products wherein the oxyalkylated hydroxylated polyamines, hereinafter described in dein which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom; the divalent radical might be not only insoluble but also infusible.

resin condensate is reacted with a member of the class of (a) compounds of the following formula:

wherein R is essentially an aliphatic hydrocarbon bridge, each n independently has one of the values 0 to 1, and R1 is an alkyl radical containing from 1 to 4 carbon atoms, or even 12 carbon atoms, and (b) cogenerically associated compounds formed in the preparation'of (a) preceding including monoepoxides.

Reference to being thermoplastic or non-thermosetting characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heat ing below the point of pyrolysis and thus difierentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from 'a reactant which is not' soluble and Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the monoepoxide-derived product. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinate solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes re ferred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxy rings or oxirane rings in the alphaomega position. This is a departure, of course, from sa /71,423v j s the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy- 3,4-epoxybutane (1,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or

components, of'the resultant orreaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinand may be entirely free from an hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble'resins and: have certain solubility characteristics not inherent in the usual thermosetting resins.

Havingobtained a reactant having generally 2, epoxy rings as depicted in the last formula preceding, or low molal polymersrthereof, it, becomes obvious the reaction can take place'with any oxyalkylated'phenol-aldehyde resin by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic'hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on'whether initially there was present a hydroxylated group attached to an amino hydrogen'group or a secondary amino group; In any'event' there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated V The compounds here included are limited to V 7 times their weight of gluconic acid at ordinary term perature and sh'ow'at least some tendency towardsbein'g self-dispersing. The solventwhich is generally tried is xylene. If xylene alone does not serve thena mixture of xylene and methanol, for instance, 80 parts of xylene and parts of methanol, or 70 parts of xylene and parts of methanol, canbe'us'ed. Sometimes it is desirableto. add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. As goxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

For purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those .products which as such or in the form of the free base or hydrate, i; e., combinationwith water or particularly in the form of a low molalorganic acid salt such as the gluconates or the acetate or-hydroxy acetate, have sufficiently hydrophil character to at least meet the test set forth'in U. S. Patent No. 2,499,368, dated March "7, 1950, to De Groote et al. In said patent such test foremul's'ification using a waterinsoluble solvent, generally xylene, is

described as an index of surface activity.

In thepresent'instance the variouscondensation products'as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some'suitable' solvent,- preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for-the reason that there will be two phases on vigorous shaking and surface activity'makes its presence manifest. It'is understood th reference, in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of. convenience, what is said hereinafter,

V will be v divided into nine parts with Part 3, in turn, being divided into, three subdivisions: Part 1 is concerned with our preferenc in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

in which the various characters have their previous signi ficance and the characterization oxyalkylated condensate is simply an abbreviation for the oxyalkyl'ated condensate which is describedin greater detail subsequently.

Suchfinal product in turn also must be soluble but solubility is not limited to an organic solvent but may include water or for that matter, a solution of water coritaining an acid-suchas hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, Whether four or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combi nation with water) or a salt form such as the acetate, chloride, etc. Th purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does Part 3, SubdivisionA, is concerned with the preparatiomof monomeric diepoxides; includingTablel Part 3, Subdivision B, is concerned with the prepar'aa tion; of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as. the monomer and includes Table II;

' Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction toyield anamine-rnqdified resin;

Part 5' is concerned with basic nonhydroxylatedpolyr amines havingat least one secondary amino group and having not over 32 carbon atoms in'any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be'free from any primary aminoradi cal, any substituted imidazoline radical, and any substituted tetrahyoropyrimidine radical; and 7 a V Part 6 is concerned with reactionsinvolvingtheresm,

' the'amine, and formaldehyde to producespecific products or compounds which are thensubjectedto oxyalkylation with monoepoxides;

per molecule.

the monomer. ;and described in the literature and will be referred-to sub- :amount of polymers present.

Part 7 is concerned withthe oxyalkylationoftheproducts describedin Part-6, preceding;

Part 8 is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more't han a reaction between two moles of a previously-prepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 9 is concerned with th resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction-products.

PART 1 As will be pointed out subsequently, the preparation 'of polyepoxides may include the formation of a small amount-of material having more thantwo epoxide groups If such compounds are formed they :are perfectly suitable except to the extent they -may ;tend to produce ultimate reaction products which are not solvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafteris largely limited to olyepoxides in the form of diepoxides.

As has been pointed. out previously one of the reactants employed is a diepoxide reactant. It is generally ob- The ordinary or conventional manufacture-of :of the monomeror separation of-the monomer from .the

remaining mass of the co-generic mixture is usuallyexpensive. If monomerswere available commercially at :a low cost, or if they could be prepared without added expense for separation, our preference would be to use Certain monomers have been prepared sequently. However, from a practical standpoint one .must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint;

thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher poly mers.

It has been pointed out previously that the phenolic .or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the 'die oxide r'ea'ctants ean "be produced in "more than one way as pointed out elsewhere, our preference is to produce them by means of the epichloroh'y- 'drin reaction referred to in detail subsequently.

- One epoxide whieh'can be-purchased intheopenm-arket and contains only a modest'amount of polymers corresponds to the'derivative of'bis-phenol A. It can be-used as such, or the monomer can 'be separated by an added step which involves additional expense. This compound of the following structure is preferred as .the epoxide reactant and will be used for illustration repeatedly with the full understandingthat any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for part, to -.wit, Part 1, and in succeeding parts,the-text. is concerned-almost entirely withaepoxides in .which there -isno bridging radical .or the bridging radical is derived from an aldehyde or :-a ketone. It would be immaterial if the divalent linking radical would .be derived from :the other groups illustrated for-the reason that nothing more than mere substitution of one compoundfor the otherwould be required. Thus, what is-saidj hereinafter,

although directed to one class or a few classes, applies with equal force and effecttothe other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed ;from,-impurities with considerable :e-a're .for the reason -that;any time that a low-molal sulfurcontaining compound can react with epichlorohydri there may be formed .a-by-product in which the. chlorine happened to beparticula-rly, reactive and may rrepresentra product, or a mixture of products, which would be {11,111-

.usua1ly toxic, .even though in comparatively small .con-

centration.

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example,

the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the presentinvention has the following structure:

H H H H H H %*?C 0 CH3 0 Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be'indicat'edby the following structure:

..H H H I -H H H Ho-o-oo oo-.oo--on l g H l H I l 01 H CH3 0H 01 Treatment with alkali, of course, fforms the epoxy ring. A number of problems are involved in attempting to produce this compound free'from "cogenericmaterials of related composition. The difficulty stems from a number of sources and a few of the more important ones are as follows:

('1) The closing of the epoxy ring involves the use of catalyst in causing the ring to open in an oxyalkylation .reaction.

.ferred ratio, to wit, two parts of epichlorohydrin to one of alkali, and for that matter in the complete absence 'tion with compounds having one, or in the present infisthe one which has been indicated previously, together with the fact that in the ordinary course of reaction a and tetramers in which two epoxide groups are present.

respond in every respect except that one terminal epoxcaustic soda or the like which, in turn, is an efiective one chlorine atom andone hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring. a ()Some'reference has been made to the presence Actually, What may happen for any one of a number of a chlorine atom and although all effort is directed of reasons is that one obtains a product in which there 5 towards the elimination of any chlorine-containing moleis only one epoxide ring and there may, as a matter of cule yet it is apparent that this is often an ideal approach fact, be more than one hydroxyl radical as illustrated by rather than a practical possibility. Indeed, the same the following compounds: sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide H H H (3H3 H H H 10 group and a chlorine atom present. See U. S. Patent Hoo-o-oo o-ooon No. 2,581,464, dated January 8, 1952, to Zech.

H H 6 For purpose of brevity, without going any further, the

next formula is in essence one which, perhaps in an or idealized way, establishes, the composition of resinous productsavailable under the name of Epon Resins as H H H CH! H H H now sold in the open market. See, also, chemical HC-CC0C C O-CCOH pamphlet entitled Epon Surface-Coating Resins, Shell H (IJH: H i 6 Chemical Corporation, New York city. The word Eponv is a registered trademark of the Shell Chemical (2) Even if one starts with the reactants in the pre- Corporation.

CH: OH CH:

0 0 1 CH2 311! u JHI CH (IJH (7H 0 C CH For the purpose of the instant invention, n may rep resent a number including zero, and at the most a low 'number such as 1, 2 or 3. This limitation does not two epichlorohydrin residues become attached to a single exist in actual efiorts to obtain resins as differentiated bis-phenol A nucleus by virtue of the reactive hydroxyls from the herein described soluble materials. It is quite present which enter into oxyalkylation reactions rather probable that in the resinous products as marketed for than ring closure reactions. coating use the value of n is usually substantially higher. (3) As is well known, ethylene oxide in the presence Note again what has been said previously that any formula is, at best, an over-simplification, or at the most of Water, forms cyclic polymers. Indeed, ethylene oxrepresents perhaps only the more important or principal ide can produce a solid polymer. This same reaction 40 constituent or constituents. These materials may vary can, and at times apparently does, take place in connecfrom simple non-resinous to complex resinous epoxides which are polyether derivatives of polyhydric phenols stance, two substituted oxirane rings, i. e., substituted containing an average of more than one epoxide group 1,2 epoxy rings. Thus, in many ways it is easier to proper molecule and free from functional groups other than duce a polymer, particularly a mixture of the monomer, epoxide and hydroxyl groups. dimer and trimer, than it is to produce the monomer In summary then in light of what has been said, comalone. pounds suitable for reaction with amines may be sum- (4) As has been pointed out previously, monoepoxmarized by the following formula:

R! ides may be present and, indeed, are almost invariably 5 or for greater simplicity the formula could be restated part of bis-phenol A, they do not necessarily so react and as a result one may obtain products in which more than in which the various characters have their prior significance and in which R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol polyepoxides, and particularly diepoxides. The reason diepoxide, such as CH: H H H H H H 7-% C %r\ .o CH3 0 'h may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text imme- 7 diately following reference is made to the dimers, trimers i i h d mpresent hydrogen and drocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and ide group is absent and in its place -is a group having .75 l, and h represents a whole number not greater than 3.

Needless to say, compounds can be formed which cor- PART 3 Subdivision A The preparation of the diepoxy derivatives of the diincluded for purpose of illustration. These particular compounds are described in the two patents just mentioned.

TABLE I EX- 7 Patent ample Diphenol Dlglycidyl ether refernumber ence s( s 4 )z Dl(epoxypropoxyphenyl)methylphenylmethan Dlgepoxypropoxyphenyl)ethylphenylmethane- Di epoxypropoxyphenyl)propylphenylmethane.

Di(epoxypropoxyphenybbutylphenylmethane 2, 506, 486 Di(epoxypropoxyphenyl)tolylmethane 2, 506, 480 Di(epoxypropoxyphenyl)tolylmethylmethane 2, 6, 486 4,4'-bis(2,3-epoxypropoxy)diphenyl 2, 530, 353

2,2-bls(4-(2,3epoxypropoxy)2-tertiarybutyl phenyl)propane-- 2, 530, 353

phenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are

Subdivision B TABLE II I c o-o- -oR1- 'R ..-R,o-c-c-c- -OR1-[R],.R10'C-C-C H: H H2 H! (I) H2 H: H H:

(in which the characters have their previous significance) Example R O from H1110 R- n 1: Remarks number 131 Hydroxy benzene CH5 1 0,1,2 Phenol known as bis-phenol A. Low I polymeric mixture about 36 or more C where 1t=0, remainder largely where l 1t'=1, some where 'n=2. CH5

B2... do CH; 1 0 ,1 ,2 Phenol known as bis-phenol B. See note 5 regarding B1 above. I CIHI CH:

B3 Orthobutylphenol CH; 1 0,1,2 Even though n is preferably 0, yet the I usual reaction product might well eon- C tain materials where 1: is 1, or to a I lesser degree 2. OH:

134..-.-- Orthoamylphenol (3H, 1 0,1,2 Do.

B5 Orthooctylphenol EH; 1 0,1,2 Do.

I CHI B6- Orthononylphenol (3H1 1 0,1,2 Do.

B7 Orthododecyl-phenol EH; 1 0,1,2 Do.,

I OH:

B8 Metacresol CH; 1 0,1,2 See prior note. This phenol used as I initial material is known as bis-phenol C C. For other suitable bis-phenols see I U. 8. Patent 2,564,191. CH3

$13; 1 0,1,2 See prior note. (l]. E

' TABLE Hammad;

Example -R Otrom HR1OH -R 1i '11 Remarks number B Dibutyl (ortho-para) phenol. 13 1 0,1 ,2 See prior note.

Bl1 Diamyl (ortho-para) phenoli 0,1,2 Do.

312", Dioc tyl (ortho-pera) phenol. g 1 0,1,2 Do.

B13 Dinonyl (ortho-para) phenol 1 0,1,2 7 Do.

B14 Dlamyl (ottho para) phenol. 1g 1 0,1,2 Do. 1.

B15 do H 1 0,1,2 Do.

B16 Hydroxy henzene Z 1 0,1,2 Do.

B17 Diamyl phenol (ortho-para)- -S-S-- 1 0, 1,2 Do.

B18 do 'S- 1 0,1,2 7 Do B19 Dibutyl phenol (ortho-para). g 1 0,1,2 Do

B20 do H 'H' 1 0,1,2 Do. VOV.C- r

B21 Dinonylphenol(orthopara). 1g 1 0,1,2 Do.

B22 Hydroxy benzene fl) 1 0, 1, 2 Do.

do None 0 0, 1,2 Do.

B24 Ortho-isopropyl phenol" CH 1 O, 1, 2 See prior note. As to preparation 0M3- isopropylidene bis-(2-isopropylphenol) see U. S. Patent No. 2,482,748, dated 5 Sept 27, 1949, to Dietzler. H: 7

B25 Para-oetyl phenol CH2SCH: 1 0, l, 2 See prior note. (As to preparation of the phenol sulfide see U; S. Patent No. 2,488,134, dated: Nov. 15, 1949, ,to 'Mikeska et a1.)

3826.---.. Hydrox-ybenzene CH; 1 i '0, l, 2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,526,545.)

( JiHa Subdivision C V The prior examples have'been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regard-- less of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other-diphenols which 'canbe readily converted to-a suitable polyepoxide, andparticularly -di-'- epoxide, reactant.

As previously pointed out the initial i;p.henol may be substituted, and the s'ubstituent 'group" in turn may be a cyclic group such as the phenyl group or c'yclohex'yl group as in the instance of cyclohcxylphenol or phenylphenol. Such substituents are usually in the o'rtho postition and may be illustrated by a phenol of the following composition: V

Similar phenols which are monofuuctional, for instance, paraphenylphenol"orparaeyclohexyl phenolwith an additional. substituent in the ortho position, may be employedin reactions previously referred to, for instance,

with formaldehyde or sulfur chlorides to give comparable 13 phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydtin, etc.

Other samples include:

wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

i CEHUOOHP OOHHH 051111 CsHn in which the --C5H11 groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

HO OH See U. S. Patent No. 2,285,563.

See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

l 1 R EUR 1 CH3 CH3 wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

I OH; CHa See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

05H C5H11 See U. S. Patent No. 2,331,448. As to descriptions of various suitable phenol sulfides, reference is made to the followings patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as Alkyl Alkyl Alkyl in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various discresol sulfides of this invention:

OH CH: CH: OH s R: R R R1 in which R1 and R2 are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R1 and R2 each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH H H C H R R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or-ldodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde-it may, of.'course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin. is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resinsare derived from trifunctional phenolsnastpreviouslymoted. However, even when obtained from,a difunctionaltphenol,for instance, paraphenylphenol one may obtain a resin which is not soluble in a nonoxygenated solvent,-'such-asbenzene or xylene, but requires anoxygenated solvent 'such as a low molal alcohol idioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as rawmaterials rmusttbe soluble .in. a. nonoxygena-ted .solvent, such as benzene or xylene. This presents no .problem insofar that. all that is required is to make ea" solubilitynestcon commercial-1y available resins, or else prepare resins whichare x-y1ene.0r benzene-soluble as-described in aforementioned .U..'S.:Batent No...2,499,'365, 01' :in ,U. Patent No. 2,499,368, dated March 7,.-1950,,to De Grootesand-Keiser. zlnsaid patent there are described oxyalkylatiomsusceptible, fusible, nonoXygenated-organic solvent-soluble, waterinsoluble, low-stage phenolaldehyde resins' having an average molecular weight corresponding to at least 3 and not over 6 phenolic -nuclei per resin-:molecule. These resins are difunctional only inr-regardzto methylol-forming reactivity, are derived by reaction between a difunc tional monohydric phenol and an aldehyde having. not over v8 carbon atoms and/reactive toward .said phenol, and. are formed in the .substantialabsence oftrifunctional Phenols; The phenol, .is, of the, fromula The basic nonhydroxylated amine may be designed thus:

".In "conducting reactions -of-' this kind "one idoes not necessariiy -"obtain a hundred percent; yield "for :obvious reasons. -"Certai'n side reactions may take-I'JIMQ I'FQ i 6 instance lmoles,oflamine may:c0mbine with one:rnoleof the aldehyde,;or..o.nly vonemole of :the aminemay combine with the resin molecule, or even/to. aver-y slight extent, if at all, 2 resin'units may combine 'without any amine in the reaction product, as indicated in the following formulas: a

As has been pointed out previously, as far as the resin unit goes one can \use a mole of aldehyde other than formaldehyde such as acetaldehyde,propionaldehyde or butyraldehyde. Theresinunitmay be exemplified thus:

V in which R'" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be. described .best in terms of the method of manufacture.

As'previously stated the preparation of resins, the kind herein employed as reactants, is well known. scepticviously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neitheracid nor-basic properties in the ordinary sense-or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence rof a =smallam ountof a free basef The amountvmaybe as srna'll as a 200th ofl aipercent and as muchas a; few'10ths of apercent. Sometimes-moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not; get a single polymer,

i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, e tc. Ibis usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may .be suchtthatit corresponds to, a fractional .valuefor ngasjforexample, 3;5,'4-.'5 orj5.2. T

"Inithe actual manufacture offthe resins; we found no reason for usingo'ther jthanthose which are: lowest in price and most readily availablecommercially. Fonpur- TABLE III Mol. Wt 151- R!!! of resin ample R Position derived n molecule number of R from- (based on n+2) Phenyl Para Formal 3. 5 .992. 5

Tertiary bntyl. 3. 5 882. 5 Secondary buty 3. 5 882. 5 Cyclo-hexyL. 3. 5 1, 025.5 Tertiary amy 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 805. 5 3. 5 1, 036. 5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 y 3. 5 1, 498. 5 Tertiary butyl i. 3. 5 945. 5

Tertiary amyl 3. 5 1,022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3, 5 1, 148. 5 N onyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

Tertiary amyl- 3.5 1, 085.5 Nonyl 3. 5 1, 393. 5 Tertiary buty 4. 2 996. 6

Tertia am 1. 4. 2 1, 083. 4 Nonyl? 4. 2 1, 430. 6 4.8 1, 094. 4 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604.0 1. 5 646. 1. 653.0 1. 5 688. 0

PART 5 As has been pointed out, the amine herein employed as a reactant is abasic secondary polyamine andjpreferably a strongly basic secondary polyamine free from hydroxyl groups,-free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl alicyclic arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from dichloride, propylene dichloride, or the like, are obtained from dichlorois ethyl ethersin which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

Another procedure for producing suitable polyamines is a reaction involving first and alkylene imine, such'as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate, or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent orthe comparable procedure in which a halide is used.

What has been said. previously may be illustrated-by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, orasecondary alicyclic-amine, such as dibu'tylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce. a primary amino group which can be :reactedwith.an-alkylat-ing agent, such as dimethyl sulfate. In a somewhat similar procedure the. secondary amine of the kind justspecified can be reacted with analkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus..an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylatingagent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula in which X is a small whole number having a value of 1 or more, and may be as much as 10.0r 12; n 1513.11 integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to 1, with the proviso that the sum of m plus m equals 2; and Rhas its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943, to

19 Hester and 2,355,337, dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CHsOCrHACl GHQ-CH1 CH: CHE-C1120 C2H4O CiNiBt Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by (CHsOCHzCHzCHzCHaCHzCHz)aNH.

Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, ootyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: betaphenoxyethylamine, gamma-phenoxypropylamine, beta-v phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an over-simplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may react to two different positions and thus the same amine may yield compounds in which R and R are dissimilar. This is illustrated by reference to two prior examples:

CH3 CH3 H NpropyleneNpropyleneN (CH3)2NGIH4NC2H4NC2H4NC2H4N(OH3)2 H H H In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a termi- Table II.

nal amino radical is not involved it is obvious again that one could obtain two difierent structures for theradicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions Where a large variety of compounds might be obtained due to such multiplicity of reactive radicals- This can be illustrated by the following formula:

0H3 /0H, NC2H4NC2H4NCzH4NCzH4N H H H 7 CH, Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general Way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are I not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed perhaps no description is necessary over and above What has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.-

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus We have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 156 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing 7 such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a lowboiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a cornparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not re- 21 quired in'the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not neces vary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which maybe the commercial product which 'isapproximately 37%,or it may be diluted down to about 30% formaldehyde. However, paraformalde'hyde can be used but it is more diflicult perhaps to add a solid material' instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced of course, by making a solution in the acidified vehicles such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any Water present by refluxing with benzene or the like.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have :not found any case Where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is .not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and --the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the pclyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. if so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble i cooled to at least the reaction temperature or somewhat below, for example 35 C. of slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difliculty with form aldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difiiculties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory proedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to 1024 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture .to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., andgenerally slightly above 100 C. and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, moiecular weight, and particularly in some instances have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

' 24 a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other ex- In light of what has been said previously, little more amples, it varied from a little over 20 hours up to 36 need be said as to the actual procedure employed for the hours. The time can be reduced by cutting the low tempreparation of the herein described condensation products. perature period to approximately 3 to 6 hours.

The following example will serve by way of illustration: Note that in Table IV following there are a large num- Exam [e M ber of added examples illustrating the same procedure.

p In each case the initial mixture was stirred and held at The Phenol-aldehyde @5111 is the 0116 that has n a fairly low temperature (30 to 40 C.) for a period of identified previously as Example 2a. It was obtained several hours. Then refluxing was employed until the from a para-tertiary butylphenol and formaldehyde. The odor of formaldehyde disappeared. After the odor of resin was prepared using an acid catalyst which was formaldehyde disappeared the phase-separating trap was completely neutrahzed at the end of the reaction. The employed to separate out all the water, both the solution molecular weight of the resin was 882.5. This correand condensation. After all the water had been separated sponded to an average of about 3 /2 phenolic nuclei, as enough xylene was taken out to have the final product the value for n which excludes the 2 external nuclei, i. e., reflux for several hours somewhere in the range of 145 the resin Was largely a mixture having 3 nuclei and 4 to 150 C., or thereabouts. Usually the mixture yielded nuclei, excluding the 2 external nuclei, or 5 and 6 overall a clear solution by the time the bulk of the water or all nuclei. The resin so obtained in a neutral state had a of the water, had been removed.

lighter amber color. Note that as pointed out previously, this procedure is 882 grams of the resin identified as 2a preceding were illustrated by 24 examples in Table IV.

TABLE IV Strength 01' Reae- Reac- Max.

Ex Resin Amt., Amine used and amount form Solvent used tion tion distill.

No us d rs. dehyde 50111. and amt. temp., time temp.,

and amt. 0. (hrs.) C.

882 Amine A, 176 g 30%, 200 g... Xylene, 600 g.-- 20-23 26 152 480 Amine A, as 30%, 100 g... Xylene, 450 g.-- 20-21 24 150 633 .do do Xylene, 550 g... 20-22 28 151 441 Amine B, 116 g..-. 37%, 81 g Xylene, 400 g... 20-28 36 144 480 do do Xylene, 450 g 22-30 156 633 do do Xylene, 600 g- 21-28 32 150 882 Amine C, 204 2.- 200 g .do 21-23 30 145 480 Amine O, 102 g 37%, 100 g Xylene, 450 g. 20-25 148 473 Amine D, 117 37%, 81 Xylene, 425 g. 20 22 31 145 511 do Xylene, 500 g 2126 24 146 665 -do Xylene, 550 1;... 22-25 36 151 441 Amine E, 158 g Xylene, 400 g 25-38 32 150 480 do .do 21-24 30 152 595 do Xylene, 550 g..- 2126 27 145 441 Amine F 191 g Xylene, 400 g 20-23 25 141 498 .do. o 32 148 542 Amine Xylene, 500 g.-- 30 148 441 do Xylene, 440 g..- 21-24 32 150 595 Amine H, 282 g Xylene, 500 g. 21-28 25 150 391 Amine H, 141 g 30%, g.. Xylene, 350 g--- 21-2 28 151 powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. This presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the Xylene was removed until the temperature reached approximately 152 C., or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture, A small amount of the sample was heated on As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

stantially' conventional for the oxyalkylation' of compounds having labilehydrogen atoms, and for that reason afdetailed' description. of the procedure is omitted and the process will simply be illustrated'by' the following examples.

Example Theoxyalkylation-susceptible' compounds employed is the one previously described and designated as Example 15. Condensate lb was in turn obtained from' symmetrh cal dimethylethyle'ne diamine and the resin'pre'vi'ously identified as example 2a. Reference to Table III shows that this'particular resin is obtained from paratertiarybutylphenol and formaldehyde. 10.82 pounds ofth'is resin condensate were dissolved in 6 pounds of solvent (xylene along with one pound offinely pow d'eredcaustic soda as a catalyst. Adjustmentwas made in' the autoclave to operate at a temperature of approximately 125 C. to 130 C-., and at a pressure of about 1-5 to m pounds, 25 pounds at the most. In some subsequent-example's pressures up to 3-5 poundswere' employed.

The time regulator was set so as to inject the ethylene oxide in approximately threequarters of an hour and then continue stirring for 15 minutes or longerya total time of one hour. Thereaction went readily and, as" a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The'speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.82 pounds. This represented a molal ratio of 24.6 moles of ethylene oxide per mole of condensate. H 1

The theoretical molecular weight at the end of the reaction period was 2164. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned'and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no' cognizance of this fact is i'n'cluded inthe-data, or subsequent data, or in the data presented in tabular form in subsequent Tables V and VI.

Thesize or the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted andisubjeo'ted tooxyalkylation with a different oxide.

This example simply illustrates the further oxyalkylatlon of Example 10, preceding. As previously stated, the oxyalkyla-tion-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the sameas at the end of the prior stage (Example is), to wit, 10.82- pounds. The amount of oxide present in the initial: stepwas 10.82 pounds, and the amount of solvent remained the same. The amount of'oxide added was another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate was 49.2 to 1. The theoretical molecular weight was 3246.

The maximum temperature during the operation was C. to C. The maximum pressure was in the range of 15 to 25 pounds. The time period was one and three-quarter hours.

Example 3c The oxyalkylation proceeded in the same manner described in Examples 1c and 2c'. There was no added solvent and no added catalyst. The oxide added was 10.82 pounds and the total oxide at the end of the oxyethylation step was 32.46 pounds. The molal ratio of oxide to condensate was 73.8 to 1. Conditions as far astemperature and pressure and time were concerned were all the same as in Examples 10' and 2c. The time period was somewhatlonger than in previous examples, to wit, 2 hours.

Example 40 The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 54-10. The molal ratio of oxideto condensate was 98.4 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer to wit, 2 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 5c 'The oxyethylation continued with the introduction of another 10.82 pounds of ethylene oxide. No more solvent-was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6492, and the molal ratio of oxide to resin condensate was 123 to 1. The time period, how- 27 ever, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

.- Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or moresolvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added to the end of this step was.86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables V and VI, VII and VIII In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables V and VI, it will be noted that compounds 1c through 400 were obtained by the use of ethylene oxide, whereas 41c through 80 were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples through 40c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the Sthcolumn is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

' The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period. 7

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VIII. It is to be noted that the first column refers to Examples 10, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure. I

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when theconcentrated material in turn is diluted with xylene separation takes place.

Referring to Table VI, Examples 41c through 800 are the counterparts of Examples lc through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously four columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VII. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series,'for example, 36c, 40c, 54c and 700. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 400 were obtained by the use of ethylene oxide it is obvious that those obtained from 360 and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 54c and 700 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, asld, 2d, 3d, etc., the initial 0 series such as 360,400, 54c, and 70c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 36c, consisted of the reaction product involving 10.82 pounds of the resin condensate, 16.23 pounds of ethylene oxide, 1.0 pounds of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table VII refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent; Reference to the solvent, refers to the total solvent present, i. e., that fromthe first oxyalkylation step plus added solvent, if any. V

i In this series, it will be noted that the theoretical molecular weights are givenprior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of thenext step, except obviously; at the very start the value 29 depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 170! through 32d. It will be noted also that under the molal ratio the 30 The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no efiort is made to obtain colorless resins initially and the resins themselves may be yellow,

values of both oxides to the resin condensate are in- 5 amber, or even dark amber. Condensation of a nieluded, V trogeneous product invariably yields a darker product The data given in regard to the operating conditions than the original resin and usually hasa reddish color. is substantially the same as before and appears in Table The solvent employed, if xylene, adds nothing to the VIII. 7 color but one may use a darker colored aromatic petro- The products resulting from these procedures may 10 leum solvent. Oxyalkylation generally tends to yield contain modest amounts, or have small amounts, of the lighter colored products and the more oxide employed solvents as indicated bythe figures in the tables. If the lighter the color of the product. Products can be desired the solvent may be removed by distillation, and prepared in which the final color is a lighter amber with particularly vacuum distillation. Such distillation also a reddish tint. Such products can be decolorized by the may remove traces or small amounts of uncombined oxuse of clays, bleaching chars, etc. As far as use in doide, if present and volatile under the conditions emmulsification is concerned, or some other industrial uses, ployed. there is no justification for the cost of bleaching the Obviously, in the use of ethylene oxide and propylproduct. v ene oxide in combination one need not first use one ox Generally speaking, the amount of alkaline catalyst ide and then the other, but one can mix the two oxides present is comparatively small and it need not be re"- and thus obtain what may be termed an indifierent oxyalmoved. Since the products per se are alkaline due to kylation, i. e., no attempt to selectively add one and then the presence of a basic nitrogen, the removal of the al'-- the other, or any other variant. kaline catalyst is somewhat more difiicult than ordinarily Needless to say, one could start with ethylene oxide is the case for the reason that if one adds hydrochloric and then use propylene oxide, and then go back to ethylacid, for example, to neutralize the alkalinity one may ene oxide; or, inversely, start with propylene oxide, then partially neutralize the basic nitrogen radical also. The use ethylene oxide, and then go back to propylene oxide; preferred procedure is to ignore the presence of the al or, one could use a combination in which butylene oxkali unless it is objectionable or else add a-stoichiometri'c' ide is used along with either one of the two oxides just amount of concentrated hydrochloric acid equal to the mentioned, or a combination of both of them. caustic soda present.

TABLE V Composition before Composition at end Molal ratio Melee. Ex. No. wt.

OS* 0S* Ethl. Propl. Oata- Sol- OS* Etbl. Propl. Cata- Sol. Ethyl. Prop]. based cmpd, cmpd., oxide, oxide, lyst, vent, empd., oxide, oxide, lyst, vent, oxide oxide on the-- ex. No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretieal alkyl. alkyl. value suseept. suscept. cmpd. empd.

1. 0 6. 0 1o. 82 1. 0 6. 0 24. 6 2,164 1. 0 6. 0 10. 82 1. o 6. 0 49. 2 3, 246 1. 0 6. o 10. 82 1. 0 6. 0 73. 8 4, 328 1. 0 6. 0 10. 82 1. 0 6. 0 98. 4 5,410 1.3 6.0 10.82 1.3 6.0 123.0 6,492 1. 3 6. 0 10. 82 1. 3 6. 0 147. 6 7, 574 1. 3 6. 0 10. 82 1. 3 6. 0 169. 2 656 1. 3 6. 0 10. 82 1. 3 6. 0 196.8 9, 738 1. 0- 4. 5 11.88 1. 0 4. 5 27. 0 2,376 1. 0 4. 5 11. 88 1. o 4. 5 54. 0 5 4' 1.0 4.5 11.88 1.0 4.5 81.0 4,752 1.0 4.5 11.88 1.0 4.5 108.0 5,940 1.3 4.5 11.88 1.3 4.5 135.0 7,128 1.3 4.5 11.88 1.3 4.5 162.0 8,316 1.3 4.5 11.88 1.3 4.5 189.0 9,504 1. 3 4. 5 11.88 1. 3 4. 5 216. 0 10, 692 1. 0 4. 25 12. 04 1. 0 4. 25 27. 4 2, 408 1. 0 4.25 12.04 1. 0 4.25 54. s 3, 612 1. 0 4. 25 12.04 1. 0 4. 25 82. 2 4, 1 1. 0 4. 25 12. 04 1. 0 4. 25 109. 6 6, 020 1. 3 4. 25 12.04 1. 3 4. 25 137. 0 7, 224 1. 3 4. 25 12.04 1. 3 4. 25 164. 4 8, 428 1. 3 4. 25 12.04 1. 3 4. 25 191. 8 9, 632 1. 3 4. 25 12.04 1. 3 4. 25 219. 2 10, 836 1. 0 5. 0 14. 56 1. 0 5. 0 33.1 2, 91-2 1. 0 5. 0 14.56 1. 0 5. 0 66. 2 4, 368 1. 0 5. 0 14.56 1. 0 5. 0 99. 3 5, 24 1. 0 5. 0 14. 56 1. 0 5. 0 132. 4 7, 280 1. 3 5. 0 14.56 1. 3 5. 0 165. 5 8. 736 1. 3 5. 0 14.56 1. 3 5. 0 198. 6 10, 192 1. 3 5. 0 14. 56 1. 3 5. 0 231. 7 11, 648 1. 3 5. 0 14.56 1. 3 5. 0 264. 8 ,104 1.0 6.0 10.82 1.0 6.0 12.3 1,623 1. 0 6. 0 10. 82 1. 0 6. 0 24. 6 164 1. o 6. 0 10. 82 1. 0 6. 0 36. 9 2, 705 1. 0 6. 0 10. 82 1. 0 6. 0 49. 2 3, 246 1. 3 6. 0 10. 82 1. 3 6. 0 61. 5 3, 7 7 1. 3 6. 0 10. 82 1. 3 6. 0 73. 8 4, 328 1. 3 6. o 10. 82 1. 3 6. 0 86.1 4, 1. 3 6. o 10. 82 1. 3 6. o 98. 4 5, 410

'Okyalkylation-susceptible.

TABLE VIII Max. Max. Solubility Ex. temp., pres., Time, No. C. p. s. 1. hrs.

Water Xylene Kerosene Insoluble.

Do. Soluble.

Do. Dispersible. Insoluble.

w res Max. Max. Solubility Ex. temp, pres, Time, No. O. p. s. 1. hrs.

Water Xylene Kerosene 5-10 5-10 5-10 5-10 5-10 5-10 5-10 Insoluble. 5-10 4 Do.

mg. Details have been ncluded in regard to both steps. PART 8 Condensate 1b, in turn, was obtained from symmetrrcal The resins condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide either one can be accomplished generally, at least in the initial stage without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 7 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be sufficient catalyst prescut for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalyst such as clay or specially prepared mineral catalysts have been used. If

for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided causticsoda or sodium methylate can be employed as a catalyst. I The amount generally employed would be 1% or 2%.-

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is not conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solventfree and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1e aration of condensate 1b was described in Part 6, preced- 7 over a period of about an hour.

dimethyl, ethylene diamine (Amine A) g the resin em;

ployed was diethanolamine and resin 2a; resin 2a, which," in turn, was obtained from para-tertiarybutylphenol and formaldehyde.

In any event, 325 grams of the oxyalkylated, resin e6 1;

densate previously identified as 20 were dissolved in approximately an equal weight of xylene. About 3 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about'3.4 grams. 17 grams of diepoxide 3A were mixed with an equal weight of xylene. Theinitial addition of the diepoxide solution -was made after raising the temperature of the reaction mass to about 107. C. The diepoxide was added slowly During this time the temperature was allowed to reflux at about 134 C. using a phase-separating trap. A small amount of xylene was removed by means. of the phaseseparating trap so the refluxing temperature rose gradually to about 160 C.

The mixture was refluxed at this temperature for about 5 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was an amber,.or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid,

but it was soluble in xylene and particularly in a mixture of 80% xylene and 20% methanol. However, if the material' was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in .a xylene-methanol mixed solvent as previously described, with -or without the further addition of a little 7 acetone.

Generally speaking, the solubility of these derivatives is in linewith expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the di- 'epoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxyethylation,

to those which conversely are water-insoluble but xylenesoluble or even kerosene-soluble due to high stage oxyjpropylation. Reactions with diepoxides or polyepoxides of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout for sake of brevity future reference to l solubility will be omitted.

The procedure employed, of course, is simple in light .Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE IX Ex. Oxy. Amt, Diep- Amt., Catalyst Xy- Molar Time of Max. I No. resin cong'rs. oxide grs. (N aOCHa), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. O.

325 3A 17 3. 4 342 2: 1 4 150 Reddish amber resinous mass. 271 3A 8 5 2.8 280 2:1 4 155 Do. 238 3A 17 2. 3 255 2:1 4 158 Do. 201 3A 8 5 3.1 310 2:1 4 150 Do. 437 3A 8 5 4.5 446 2:1 5 152 Do. 325 3A 17 3. 4 342 2; 1 5 155 Do. 379 3A 5 3. 9 388 2: 1 5 156 Do. 238 3A 17 2. 6 255 2:1 4 150 Do. 421 3A 8.5 4.3 430 21 5 148 Do. 364 3A 8. 5 3. 7 373 2:1 5 154 Do. 379 3A 17 4. 396 2 1 152 Do. 243 3A 8. 5 2. 5 252 2: 1 5 154 Do. 428 3A 8. 5 4. 4 437 2:1 5 150 Do. 406 3A 8.5 4. 2 415 2:1 5 150 Do. 180 8A 1. 7 1. 3 182 2:1 4 150 Do.

TABLE X Ex. Oxy. Amt, Dlep- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOOHa), lene, ratio reaction, temp, Color and physical state densate used grs. grs. hrs. 0.

2c 325 B1 27. 6 3. 5 358 2:1 4 140 Reddish amber resinous mass.

271 B1 13. 3 2. 9 285 2:1 3. 5 142 Do. 238 B1 27. 5 2. 7 266 2:1 3. 5 140 Do 301 B1 13. s 3. 2 315 2: 1 3. 5 145 Do. 437 B1 13.8 4. 5 451 2: 1 4 145 Do. 325 B1 27.5 3. 5 353 2:1 4 147 Do 379 B1 13.8 3. 9 393 2: 1 4 140 Do 238 B1 27.5 2. 7 265 2: 1 4 145 Do 421 B1 13. s 4.4 435 2: 1 4 145 Do 364 B1 13. 8 3. 8 378 2: 1 4 150 Do 379 B1 27.5 4.1 407 2: 1 4 148 Do 243 B1 18.8 2. 6 257 2:1 3. 5 146 Do 428 B1 13.8 4. 4 442 211 3. 5 140 Do 403 B1 13. s 4. 2 420 2:1 3. 5 145 Do. 3 d 180 B1 2.8 1.8 183 2:1 145 D0.

TABLE XI 35 or their equivalent. Dilute the resin or the diepoxide, or both with an mert solvent, such as xylene or the like. Prob mo} In some instances an oxygenated solvent, such as the 114.145. Oxyalkyl. weightoi Amount 01 Amountof diethylether of ethylene/glycol m be p y g gg g p grs. Solvent other procedure which is helpful 15 to reduce the amount p 0 c of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling sol- 6,830 3, 415 1, 70s 11,160 2,232 1,115 vent, such as benzene, or use benzene entlrely. Also, We 338 2% have found it desirable at times to use slightly less than 171310 3:552 1:731 apparently the theoretical amount of diepoxide, for ing igg 2 3, g2; stance, 90% to 95% instead of 100%. The reason for 51090 :54 1:273 this fact may reside in the possibility that the molecular E 388 2' gig 1 138 weight dimensions on either the resin molecule or the 71910 1 95 11973 diepoxide molecule actually may vary from the true 3 228 238 F 2? molecular weight by several percent. 16: 570 3:314 1:657 The condensate can be depicted in a simplified form 361340 34634 1'817 which, for convenience, may be shown thus:

(Amine CH2 (Resin) CH2 (Amine) TABLE XII If such product is subjected to oxyalkylation, reaction involves the phenolic hydroxyls of the resin structure and, Prob. mol. thus can be de icted in the followin manner: Ex. No. Oxyalkyl. weight of Anouiit 0t Armlmnt of p g resin conreac ion pro uc grs. so vent densate product (Am1ne)CH2(Oxyalkylated Res1n)CHz(Am1ne) Following such simplification the reaction with a poly- 7,040 3,520 1,760 epoxide, and partially a diepoxide, would be depicted 11,370 2,274 1,137 thus. 33 2'23 1 828 802 (Ammo)OH (Oxyalkyl2ited Resm)CH (Amine) 0 1, 760 15,700 3,140 1,570 D G E (Aminewflzwxyalkylated Resin)CH (Amine) ig ggg gg 9% in which D.G.E. represents a diglycidyl ether as specified. 161750 3:350 11575 As has been pointed out previously the condensation I550 11823 reaction may produce other products, including, for ex- At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures ample, a product which may be indicated thus in light of what has been said previously:

[(Amine)CH2(Resin)] [Oxyalkylated (Amine CH2 (Resin 7 When a diglycidyl ether is employed one would ob viously obtain compounds in which two molecules of the kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

Oxyalkylated (Amine) OH; (Resin) I l' 'l non.

Oxyalky1ated(Arnine) CH (Resin) I Likewise, it is obvious that the two difierent types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

I (Amine)CHAOxyalkylated'Resin)OHAAmine) i Oxyalkylated(Amine)CHAResiu) Oxyalkylated (Amine) CH (Amine) D.G.E.

l i (Amine)CH (Oxyalkylated Resin)CHz(Amine) Oxyalkylated (Amine) H (Amine) i Oxya1l ylated(Arnine) CH (Resin) Oxyalkylated (Amine) 0 H (Amine) i OxyalkylateMAmine)OH2(Amine) I PART 9 Conventional demusifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthraeene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol,.ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may beemployed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone orin' admixture with other suitable well-known classes of .demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland Water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of l to 10,000

or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or

1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact istrue in regard to the material or materials employed as the demulsifying agent of our process. I 1

In practicing the present process, the treating or demulsifying agent is used in the conventional Way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-theintroducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 3e with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 32, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonie acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulionic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described our invention what We claim as new and desire to secure by Letters Patent is: V

l. A process for breaking petroleum'ernulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier. being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunetional only in regard to methylol-forming reactivity; 'said resin being derived by reaction between a difunetional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A THREE-STEP MANUFACTUREING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 